CN115028942A - 一种带有保护套的抗冲击架空绝缘导线及其制备方法 - Google Patents
一种带有保护套的抗冲击架空绝缘导线及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种带有保护套的抗冲击架空绝缘导线及其制备方法,属于防护电缆技术领域。该绝缘导线包括导电绞线及其表面的抗冲击胶套,抗冲击胶套包括:抗冲击助剂2.2‑3.5wt%、润滑剂0.6‑0.9wt%、偶联剂0.1‑0.2wt%、无机填料0.5‑2wt%、颜料≤1.5wt%、液体丁腈橡胶8.2‑12.5wt%、促进剂0.1‑0.15wt%,余量为PVC树脂;抗冲击助剂的分子呈现哑铃状立体结构,降低PVC分子间作用力,提高PVC的抗冲击性,其端部含有支状甲酯,与PVC基体有良好的相容性,使得端部牢固的嵌入在PVC基体中,不易迁移析出。
Description
技术领域
本发明属于防护电缆技术领域,具体地,涉及一种带有保护套的抗冲击架空绝缘导线及其制备方法。
背景技术
随着经济的发展,需要使用电缆的场所变得多样化,对电缆用护套材料的性能指标有了更加严格和多样的要求;现有的电缆保护套多数使用PVC材料,其原料广泛、价格低廉且化学性能稳定,但是其存在一个致命缺陷,即质地脆,抗冲击性差,纯PVC制品的缺口冲击强度只有2.2KJ/m2,应用在导线保护层易破损漏电,目前对于PVC的抗冲击改性方法主要有三类:
其一,向PVC中加入无机刚性粒子增韧,其在PVC中产生“空穴增韧”,能够一定程度上提高PVC的抗冲击性,但是降低PVC的柔性,一般应用在管材和结构件中,不适用于导线的防护;
其二,向PVC中加入有机聚合物共混,较为成熟的有ACR体系和EVA体系,但是存在矛盾之处,添加大分子聚合物,相容性不好,难以达到均匀的增韧效果,添加小分子增韧剂,耐迁移性不好,难以达到稳定的增韧效果;
其三,对PVC进行进一步氯化改性处理,氯含量一般为65%-72%,抗冲击性得到改善,但是氯化工艺复杂且不易控制,难以适应加工型企业生产。
发明内容
为了解决背景技术中提到的技术问题,本发明的目的在于提供一种带有保护套的抗冲击架空绝缘导线及其制备方法。
本发明的目的可以通过以下技术方案实现:
一种带有保护套的抗冲击架空绝缘导线,包括导电绞线及其表面的抗冲击胶套,所述抗冲击胶套包括如下原料:
抗冲击助剂2.2-3.5wt%、润滑剂0.6-0.9wt%、偶联剂0.1-0.2wt%、无机填料0.5-2wt%、颜料≤1.5wt%、液体丁腈橡胶8.2-12.5wt%、促进剂0.1-0.15wt%,余量为PVC树脂;
所述抗冲击助剂由以下方法制备:
步骤A1:向干燥的反应器内投加氯化亚砜和甲苯混合,搅拌状态下投加聚己内酯二醇和丙烯酸,升温至40-50℃,搅拌速率为80-120rpm,反应2-3h,反应结束减压旋蒸,制成双键封端中间体,其结构如下:
进一步地,聚己内酯二醇、丙烯酸、氯化亚砜和甲苯的用量比为0.1mol:0.21mol:1.6-2mL:30-35mL。
步骤A2:将二乙醇胺和甲醇钠投加到反应器混合,升温至32-38℃,在360-480rpm搅拌下,将双键封端中间体溶于甲醇缓慢投加到反应器内,投加后再加入吩噻嗪混合,保温搅拌反应3-5h,双键和仲胺加成反应,反应结束用去离子水洗涤数次,制成双支中间体,其结构如下:
进一步地,步骤A2中,双键封端中间体、二乙醇胺、甲醇钠、吩噻嗪和甲醇的用量比为45-52g:21-27mL:1.5-2g:0.7-1.1g:40-50mL。
步骤A3:取双支状中间体、马来酸酐和DMF投加到反应器内搅拌溶解,升温至70℃,投加对甲苯磺酸,保温搅拌反应30-40min,再投加二乙醇胺,升温至90℃,搅拌反应60-90min,反应结束投加去离子水洗涤旋蒸数次,制成多支中间体,其结构如下:
进一步地,步骤A3中,双支状中间体、马来酸酐、二乙醇胺、对甲苯磺酸和DMF的用量比为65-75g:41-45g:48-56mL:2.2-3.0g:80-110mL。
步骤A4:取多支中间体、甲酸、四氢呋喃和浓硫酸混合后投加到反应器内,升温至70℃回流反应5-8h,反应结束投加到水中洗涤分液,取有机相脱水,制成抗冲击助剂,其结构如下:
进一步地,多支中间体、甲酸、四氢呋喃和浓硫酸的用量比为140-150g:36-45mL:50-70mL:8-10mL。
一种带有保护套的抗冲击架空绝缘导线的制备方法,具体包括如下步骤:
步骤S1:将抗冲击助剂、润滑剂、偶联剂、促进剂、无机填料和颜料混合,制成功能混合料;
步骤S2:将PVC树脂和液体丁腈橡胶投加到密炼釜内,加入功能混合料混合均匀,升温至165℃,高速剪切密炼10-15min,制成复合胶料;
步骤S3:将复合胶料挤出包覆在导电绞线表面,经过连续热空气硫化形成抗冲击胶套,完成抗冲击胶套和导电绞线复合,制成带有保护套的抗冲击架空绝缘导线。
本发明的有益效果:
1.本发明在PVC基树脂中添加一种抗冲击助剂,其由长链状的聚己内酯二醇为原料,通过丙烯酸与其酯化反应,对端部引入双键封端,提高端部活性,再将端部的双键与二乙醇胺加成,制成端部含有双支羟基结构的中间体,再经过马来酸酐开环桥接,与二乙醇胺酯化制成端部具有多支状羟基结构的中间体,最后用甲酸酯化封端,甲酯与PVC基体有良好的相容性,使得端部含有支状甲酯的抗冲击助剂可以牢固地嵌入在PVC基体中,此外,抗冲击助剂的分子呈现哑铃状,不易在PVC基体中迁移析出,哑铃状立体结构降低PVC分子间作用力,提高PVC的抗冲击性,经测试,缺口冲击强度达到11.62-12.17KJ/m2,且在60℃老化处理后保留良好的耐冲击性。
2.本发明抗冲击助剂与PVC树脂共混的方式改善架空绝缘导线保护套的抗冲击性,生产工艺简单,适用于加工型企业生产。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
本实施例制备抗冲击助剂,具体实施过程如下:
a1:取干燥污水的烧瓶投加氯化亚砜和甲苯搅拌混合5min,保持搅拌状态,向烧瓶中投加聚己内酯二醇和丙烯酸,水浴升温至40℃,设置搅拌速率为80rpm,反应3h,反应结束减压旋蒸,旋蒸温度为80℃,制成双键封端中间体,其中聚己内酯二醇、丙烯酸、氯化亚砜和甲苯的用量比为0.1mol:0.21mol:1.6mL:30mL;
a2:取二乙醇胺和甲醇钠投加到烧瓶中搅拌混合10min,水浴升温至32℃,设置搅拌速率为360rpm,将双键封端中间体和甲醇在烧杯中预先搅拌混合,然后缓慢加入烧瓶中,再投加少量吩噻嗪作为阻聚剂,防止双键封端中间体自体聚合,之后保温搅拌反应5h,反应结束加入反应液体积0.5倍的去离子水重复洗涤分液两次,制成双支中间体,其中,双键封端中间体、二乙醇胺、甲醇钠、吩噻嗪和甲醇的用量比为45g:21mL:1.5g:1.1g:40mL;
a3:将双支状中间体、马来酸酐和DMF投加到烧瓶中搅拌溶解,油浴升温至70℃,投加对甲苯磺酸,设置搅拌速率为180rpm,保温搅拌反应30min,之后再投加二乙醇胺,再升温至90℃,保温搅拌反应90min,反应结束投加反应液体积0.2倍的去离子水重复旋蒸3次,制成多支中间体,其中,双支状中间体、马来酸酐、二乙醇胺、对甲苯磺酸和DMF的用量比为65g:41g:48mL:2.2g:80mL;
a4:将多支中间体、甲酸、四氢呋喃和浓硫酸混合后投加到烧瓶中混合,安装回流冷凝器,升温至70℃回流反应5h,反应结束投加到水中洗涤分液,取有机相真空脱水,制成抗冲击助剂,其中,多支中间体、甲酸、四氢呋喃和浓硫酸的用量比为150g:45mL:70mL:10mL。
实施例2
本实施例制备抗冲击助剂,具体实施过程如下:
a1:取干燥污水的烧瓶投加氯化亚砜和甲苯搅拌混合5min,保持搅拌状态,向烧瓶中投加聚己内酯二醇和丙烯酸,水浴升温至45℃,设置搅拌速率为100rpm,反应2.5h,反应结束减压旋蒸,旋蒸温度为80℃,制成双键封端中间体,其中聚己内酯二醇、丙烯酸、氯化亚砜和甲苯的用量比为0.1mol:0.21mol:1.8mL:33mL;
a2:取二乙醇胺和甲醇钠投加到烧瓶中搅拌混合10min,水浴升温至36℃,设置搅拌速率为360rpm,将双键封端中间体和甲醇在烧杯中预先搅拌混合,然后缓慢加入烧瓶中,再投加少量吩噻嗪作为阻聚剂,防止双键封端中间体自体聚合,之后保温搅拌反应4h,反应结束加入反应液体积0.5倍的去离子水重复洗涤分液两次,制成双支中间体,其中,双键封端中间体、二乙醇胺、甲醇钠、吩噻嗪和甲醇的用量比为48g:25mL:1.8g:0.9g:45mL;
a3:将双支状中间体、马来酸酐和DMF投加到烧瓶中搅拌溶解,油浴升温至70℃,投加对甲苯磺酸,设置搅拌速率为180rpm,保温搅拌反应35min,之后再投加二乙醇胺,再升温至90℃,保温搅拌反应80min,反应结束投加反应液体积0.2倍的去离子水重复旋蒸3次,制成多支中间体,其中,双支状中间体、马来酸酐、二乙醇胺、对甲苯磺酸和DMF的用量比为70g:43g:52mL:2.6g:95mL;
a4:将多支中间体、甲酸、四氢呋喃和浓硫酸混合后投加到烧瓶中混合,安装回流冷凝器,升温至70℃回流反应6.5h,反应结束投加到水中洗涤分液,取有机相真空脱水,制成抗冲击助剂,其中,多支中间体、甲酸、四氢呋喃和浓硫酸的用量比为145g:41mL:60mL:9mL。
实施例3
本实施例制备抗冲击助剂,具体实施过程如下:
a1:取干燥污水的烧瓶投加氯化亚砜和甲苯搅拌混合5min,保持搅拌状态,向烧瓶中投加聚己内酯二醇和丙烯酸,水浴升温至50℃,设置搅拌速率为120rpm,反应2h,反应结束减压旋蒸,旋蒸温度为80℃,制成双键封端中间体,其中聚己内酯二醇、丙烯酸、氯化亚砜和甲苯的用量比为0.1mol:0.21mol:2mL:35mL;
a2:取二乙醇胺和甲醇钠投加到烧瓶中搅拌混合10min,水浴升温至38℃,设置搅拌速率为480rpm,将双键封端中间体和甲醇在烧杯中预先搅拌混合,然后缓慢加入烧瓶中,再投加少量吩噻嗪作为阻聚剂,防止双键封端中间体自体聚合,之后保温搅拌反应3h,反应结束加入反应液体积0.5倍的去离子水重复洗涤分液两次,制成双支中间体,其中,双键封端中间体、二乙醇胺、甲醇钠、吩噻嗪和甲醇的用量比为52g:27mL:2g:0.7g:50mL;
a3:将双支状中间体、马来酸酐和DMF投加到烧瓶中搅拌溶解,油浴升温至70℃,投加对甲苯磺酸,设置搅拌速率为180rpm,保温搅拌反应40min,之后再投加二乙醇胺,再升温至90℃,保温搅拌反应60min,反应结束投加反应液体积0.2倍的去离子水重复旋蒸3次,制成多支中间体,其中,双支状中间体、马来酸酐、二乙醇胺、对甲苯磺酸和DMF的用量比为75g:45g:56mL:3.0g:110mL;
a4:将多支中间体、甲酸、四氢呋喃和浓硫酸混合后投加到烧瓶中混合,安装回流冷凝器,升温至70℃回流反应8h,反应结束投加到水中洗涤分液,取有机相真空脱水,制成抗冲击助剂,其中,多支中间体、甲酸、四氢呋喃和浓硫酸的用量比为140g:36mL:50mL:8mL。
以下实施例制备带有保护套的抗冲击架空绝缘导线,原料选取如下:
导电绞线:选自1kv多股铝绞线;
润滑剂:选自硬脂酸钙和聚乙烯蜡按照重量比为1:3混合而成;
偶联剂:选自硅烷偶联剂KH550;
无机填料:选自活性碳酸钙和钛白粉按照重量比为5:1混合而成,粒径≤80μm;
颜料:选自工业炭黑颜料;
液体丁腈橡胶:粘度(25℃)300±10%Pa.s;
促进剂:选自CBS-80;
PVC树脂:黏数为80±5,疏松型树脂。
实施例4
本实施例制备带有保护套的抗冲击架空绝缘导线,具体实施过程如下:
s1:按照以下配比取料:
抗冲击助剂2.2wt%、润滑剂0.6wt%、偶联剂0.1wt%、无机填料0.5wt%、颜料1.5wt%、液体丁腈橡12.5wt%、促进剂0.15wt%,余量为PVC树脂
s2:将抗冲击助剂、润滑剂、偶联剂、促进剂、无机填料和颜料在混料釜中以600rpm混合20min,制成功能混合料;
S3:将PVC树脂和液体丁腈橡胶投加到密炼釜内,加入功能混合料混合均匀,升温至165℃,以2000rpm高速剪切密炼10min,制成复合胶料;
s4:将复合胶料以18MPa挤出包覆在导电绞线表面,之后经过连续热空气硫化,冷却定型后形成抗冲击胶套,制成带有保护套的抗冲击架空绝缘导线。
实施例5
本实施例制备带有保护套的抗冲击架空绝缘导线,具体实施过程如下:
s1:按照以下配比取料:
抗冲击助剂3.1wt%、润滑剂0.7wt%、偶联剂0.15wt%、无机填料1.3wt%、颜料1.5wt%、液体丁腈橡胶10.8wt%、促进剂0.12wt%,余量为PVC树脂
s2:将抗冲击助剂、润滑剂、偶联剂、促进剂、无机填料和颜料在混料釜中以600rpm混合20min,制成功能混合料;
S3:将PVC树脂和液体丁腈橡胶投加到密炼釜内,加入功能混合料混合均匀,升温至165℃,以2000rpm高速剪切密炼13min,制成复合胶料;
s4:将复合胶料以18MPa挤出包覆在导电绞线表面,之后经过连续热空气硫化,冷却定型后形成抗冲击胶套,制成带有保护套的抗冲击架空绝缘导线。
实施例6
本实施例制备带有保护套的抗冲击架空绝缘导线,具体实施过程如下:
s1:按照以下配比取料:
抗冲击助剂3.5wt%、润滑剂0.9wt%、偶联剂0.2wt%、无机填料2wt%、颜料1.5wt%、液体丁腈橡胶8.2wt%、促进剂0.1wt%,余量为PVC树脂
s2:将抗冲击助剂、润滑剂、偶联剂、促进剂、无机填料和颜料在混料釜中以600rpm混合20min,制成功能混合料;
S3:将PVC树脂和液体丁腈橡胶投加到密炼釜内,加入功能混合料混合均匀,升温至165℃,以2000rpm高速剪切密炼15min,制成复合胶料;
s4:将复合胶料以18MPa挤出包覆在导电绞线表面,之后经过连续热空气硫化,冷却定型后形成抗冲击胶套,制成带有保护套的抗冲击架空绝缘导线。
为了便于测试抗冲击胶套对铝绞线的防护作用,将实施例4-实施例6制成的复合胶料采用相同的压力和硫化工艺制成片材,进行相关性能测试,具体测试数据如表1所示:
表1
测试标准 | 实施例4 | 实施例5 | 实施例6 | |
拉伸强度/MPa | GB/T1040.1-2018 | 53.68 | 52.16 | 50.32 |
缺口冲击强度/KJ·m<sup>-2</sup> | GB/T1843-2008 | 11.62 | 12.85 | 12.17 |
维卡软化温度/℃ | GB/T1633-2000 | 82.1 | 81.6 | 79.8 |
由表1数据可知,本发明制备的PVC基抗冲击胶套的维卡软化温度为79.8-82.1℃,拉伸强度为50.32-53.68MPa,软化温度和强度适用于导线的防护,缺口冲击强度达到11.62-12.17KJ/m2,相较于现有的PVC防护胶套有明显提升。
为了验证抗冲击助剂的耐热迁移,制备试样,放置于60℃老化箱内,分别在10d、20d和30d测试缺口冲击强度,具体测试数据如表2
表2
由表2数据可知,本发明制备的PVC基抗冲击胶套在60℃下加速试验后仍保留良好的耐冲击性。
在说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
以上内容仅仅是对本发明所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (8)
1.一种带有保护套的抗冲击架空绝缘导线,包括导电绞线及其表面的抗冲击胶套,其特征在于,抗冲击胶套以PVC树脂为基体,添加有2.2-3.5wt%的抗冲击助剂;
所述抗冲击助剂由以下方法制备:
步骤A1:取氯化亚砜和甲苯混合,搅拌状态下投加聚己内酯二醇和丙烯酸,升温至40-50℃,搅拌速率为80-120rpm,反应2-3h,反应结束减压旋蒸,制成双键封端中间体;
步骤A2:取二乙醇胺和甲醇钠投加到反应器混合,升温至32-38℃,在360-480rpm搅拌下,依次投加双键封端中间体的甲醇溶解液和吩噻嗪,保温搅拌反应3-5h,反应结束用去离子水洗涤数次,制成双支中间体;
步骤A3:取双支状中间体、马来酸酐和DMF搅拌溶解,升温至70℃,投加对甲苯磺酸,保温搅拌反应30-40min,再投加二乙醇胺,升温至90℃,搅拌反应60-90min,反应结束投加去离子水洗涤旋蒸数次,制成多支中间体;
步骤A4:取多支中间体、甲酸、四氢呋喃和浓硫酸混合,升温至70℃回流反应5-8h,反应结束投加到水中洗涤分液,取有机相脱水,制成抗冲击助剂。
2.根据权利要求1所述的一种带有保护套的抗冲击架空绝缘导线,其特征在于,聚己内酯二醇、丙烯酸、氯化亚砜和甲苯的用量比为0.1mol:0.21mol:1.6-2mL:30-35mL。
3.根据权利要求2所述的一种带有保护套的抗冲击架空绝缘导线,其特征在于,步骤A2中,双键封端中间体、二乙醇胺、甲醇钠、吩噻嗪和甲醇的用量比为45-52g:21-27mL:1.5-2g:0.7-1.1g:40-50mL。
4.根据权利要求3所述的一种带有保护套的抗冲击架空绝缘导线,其特征在于,步骤A3中,双支状中间体、马来酸酐、二乙醇胺、对甲苯磺酸和DMF的用量比为65-75g:41-45g:48-56mL:2.2-3.0g:80-110mL。
5.根据权利要求4所述的一种带有保护套的抗冲击架空绝缘导线,其特征在于,多支中间体、甲酸、四氢呋喃和浓硫酸的用量比为140-150g:36-45mL:50-70mL:8-10mL。
6.根据权利要求5所述的一种带有保护套的抗冲击架空绝缘导线,其特征在于,抗冲击胶套中还包括:润滑剂0.6-0.9wt%、偶联剂0.1-0.2wt%、无机填料0.5-2wt%、颜料≤1.5wt%、液体丁腈橡胶8.2-12.5wt%、促进剂0.1-0.15wt%。
7.根据权利要求6所述的一种带有保护套的抗冲击架空绝缘导线,其特征在于,无机填料为活性碳酸钙和钛白粉按照重量比为5:1混合而成,粒径≤80μm。
8.根据权利要求7所述的一种带有保护套的抗冲击架空绝缘导线的制备方法,其特征在于,包括如下步骤:
步骤S1:将抗冲击助剂、润滑剂、偶联剂、促进剂、无机填料和颜料混合,制成功能混合料;
步骤S2:将PVC树脂和液体丁腈橡胶投加到密炼釜内,加入功能混合料混合均匀,升温至165℃,高速剪切密炼10-15min,制成复合胶料;
步骤S3:将复合胶料挤出包覆在导电绞线表面,经过连续热空气硫化形成抗冲击胶套,制成带有保护套的抗冲击架空绝缘导线。
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CN101875747A (zh) * | 2009-04-28 | 2010-11-03 | 杭州德裕饰品有限公司 | 一种超低温聚氯乙烯改性、绝缘护套电缆料及其制备方法 |
CN102993602A (zh) * | 2012-11-27 | 2013-03-27 | 宁波一舟塑胶有限公司 | 一种cmp级阻燃抑烟聚氯乙烯线缆护套料及其制备方法 |
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CN116082769A (zh) * | 2023-03-22 | 2023-05-09 | 甘肃金川恒信高分子科技有限公司 | 一种环保型聚氯乙烯复合材料及其制备方法 |
CN116082769B (zh) * | 2023-03-22 | 2023-06-27 | 甘肃金川恒信高分子科技有限公司 | 一种环保型聚氯乙烯复合材料及其制备方法 |
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